JPWO2009157445A1 - Iron alloy article, iron alloy member and manufacturing method thereof - Google Patents

Abstract

An iron alloy article having an excellent bonding force between a resin and an iron alloy using an alkoxysilane-containing triazine thiol and a method for producing the same are provided. An iron alloy article comprising a base made of iron or an iron alloy and a resin bonded to at least a part of the surface of the base via a dehydrated silanol-containing triazine thiol derivative coating, the base and the dehydrated silanol-containing triazine thiol An iron alloy having a metal compound film containing at least one selected from the group consisting of hydroxide, carboxylate, phosphate, sulfate, thiosulfate, chloride and perchloride between the derivative coating It is an article.

Description

  The present invention relates to an iron alloy article including iron and steel (including stainless steel) in which a resin is bonded to at least a part of the surface, and iron subjected to a surface treatment to cover at least a part of the surface with the resin. More particularly, the present invention relates to an iron alloy article and an iron alloy member that are excellent in adhesion between a resin and an iron alloy substrate, and a method for producing the same.

  Iron and iron alloys (the iron alloy in this specification is a concept including steel naturally, and steel includes stainless steel) have high strength and rigidity and are widely used as industrial materials. Further, an iron alloy article in which a resin is bonded to at least a part of the surface of the iron alloy substrate cannot be obtained by the resin molded product alone with the iron alloy substrate, and has a high rigidity and cannot be formed by the iron alloy alone with the resin. It is possible to obtain shape and aesthetics, and it is used in many fields including the aforementioned applications.

  Conventionally, a method of fixing a resin to an iron alloy substrate by providing a notch or a perforation in the iron alloy substrate in advance and performing in-mold molding of the resin on the iron alloy substrate by, for example, injection molding. Is used.

  However, in this method, it is necessary to secure a place where a notch or a perforation is to be provided, and there is a problem that design restrictions are large, and a bonding force does not act between the resin and the substrate except for the notch or the perforated part. Therefore, there is a problem that a gap may be generated between the base and the resin. Therefore, in this method, since the iron alloy substrate and the resin are not completely integrated, the deformable resin portion is easily deformed when a deformation stress is applied, and the rigidity of the iron alloy substrate cannot be utilized. In some cases, it is not possible to ensure rigidity that cannot be obtained by a resin molded product using an iron alloy substrate alone.

  Therefore, an acidic surface treatment agent is brought into contact with the surface of the metal material and coated on the surface of the metal material as a method that does not require notches or perforations and can apply a bonding force over the entire bonding surface between the resin and the substrate. After forming a layer and then peeling off part or all of the coating layer, a resin composition containing a silane coupling agent is applied and dried, and then an aqueous adhesive primer for rubber / metal and rubber / metal A rubber-metal bonding method (Patent Document 1) has been proposed in which a water-based adhesive is applied and dried to vulcanize and bond a rubber material.

Furthermore, in order to improve the adhesion between the lead frame for semiconductor packages and the sealing material, the surface of the iron alloy material of the lead frame material is a roughened surface having fine irregularities by dull roll rolling or etching, and the arithmetic average roughness thereof is A method of forming a sealing material of thermosetting resin such as epoxy resin on the surface area of 0.05 to 0.8 μm and a surface area alternative value of 1.005 to 1.08, and connector metal In order to increase the adhesive strength when in-mold molding the terminal and the resin holding part, the surface of the metal part is surface-treated with triazine thiols in advance, or the oxidizing power so that the surface roughness Ra becomes 1 to 10 μm. Multi-functional after micro-etching with an etching solution such as strong permanganic acid aqueous solution or forming an oxide film on the surface with an oxidizing agent There has been proposed a method (Patent Document 3) in which a nylon resin containing a functional monomer is molded and integrated, and the nylon resin is crosslinked by radiation and subjected to heat treatment at 100 ° C. or higher.
JP 2001-260235 A Japanese Patent Publication No. 10-270629 JP 2001-047462 A

  However, the above method has a problem that the process is too complicated, and the applicable resin is limited to rubber, thermosetting resin and nylon resin.

  In particular, when a method of introducing a reactive functional group on a metal surface using triazine thiol is used for joining an iron alloy and a resin, the obtained joining strength is higher than that of joining a metal such as a copper alloy and a resin. There was a problem of being low.

  Accordingly, an object of the present invention is to provide an iron alloy article having an excellent bonding force between a resin and an iron alloy using an alkoxysilane-containing triazine thiol and a method for producing the same. Another object of the present invention is to provide an iron alloy member for bonding a resin to the surface and to provide a manufacturing method thereof.

  The present invention relates to an iron alloy article comprising a base made of iron or an iron alloy and a resin bonded to at least a part of the surface of the base via a dehydrated silanol-containing triazine thiol derivative coating, the dehydrated silanol-containing triazine Including a metal compound containing at least one selected from the group consisting of hydroxide, carboxylate, phosphate, sulfate, thiosulfate, chloride and perchloride between the thiol derivative coating and It is a featured iron alloy article.

  The present invention is also a method for producing an iron alloy article, in which a resin is bonded to at least a part of an iron alloy substrate made of iron or an iron alloy using an alkoxysilane-containing triazine thiol derivative, the surface of the iron alloy substrate At least part of at least one selected from the group consisting of carboxylic acid, carboxylate, phosphoric acid, phosphate, sulfuric acid, sulfate, thiosulfate, hydrochloric acid, chloride, perchloric acid and perchlorate A step of forming a metal compound film using a solution containing two, a step of bringing the alkoxysilane-containing triazine thiol derivative into contact with the metal compound film, and bonding a resin to a portion where the alkoxysilane-containing triazine thiol derivative is in contact It is a manufacturing method characterized by including the process to do.

  The present invention further includes a base made of iron or an iron alloy, and an iron alloy member in which at least a part of the surface of the base is coated with a dehydrated silanol-containing triazine thiol derivative or a silanol-containing triazine thiol derivative, the base and the base Between the dehydrated silanol-containing triazine thiol derivative coating or the silanol-containing triazine thiol derivative coating, from the group consisting of hydroxide, carboxylate, phosphate, sulfate, thiosulfate, chloride and perchlorate An iron alloy member comprising a metal compound film containing at least one selected.

  The present invention is also a method for producing an iron alloy member in which an alkoxysilane-containing triazine thiol derivative is brought into contact with at least a portion of an iron alloy substrate made of iron or an iron alloy, wherein at least a portion of the surface of the iron alloy substrate. And a solution containing at least one selected from the group consisting of carboxylic acid, carboxylate, phosphoric acid, phosphate, sulfuric acid, sulfate, thiosulfate, hydrochloric acid, chloride, perchloric acid and perchloride And a step of forming a metal compound film, and a step of bringing the metal compound film into contact with an alkoxysilane-containing triazine thiol derivative.

  According to the present invention, a metal compound film is introduced on the surface of an iron alloy substrate, and a reactive functional group is introduced on the surface of the metal compound film using an alkoxysilane-containing triazine thiol derivative (for example, an alkoxysilane-containing triazine thiol metal salt). As a result, it is possible to provide an iron alloy member capable of bonding a resin to the surface thereof with a high bonding force, an iron alloy article having a high bonding strength between the iron alloy substrate and the resin, and a manufacturing method thereof. Become.

It is sectional drawing of the iron alloy article which concerns on this invention. It is sectional drawing of the conventional iron alloy article.

  1 Iron alloy substrate, 2 metal compound film, 3 dehydrated silanol-containing triazine thiol derivative film, 4 resin

  The inventors of the present invention have examined the reason why a sufficiently high bonding force cannot be obtained even when using an alkoxysilane-containing triazine thiol derivative when bonding an iron alloy substrate and a resin. It was found that there is a high possibility that it is caused by the surface oxide film.

  When a metal and a resin are bonded using an alkoxysilane-containing triazine thiol derivative, the alkoxysilane part chemically bonds to the metal, and a reactive functional group composed of the triazine thiol derivative part is introduced onto the metal surface. This functional group (triazine thiol derivative part) is chemically bonded to the resin, so that the dehydrating silanol-containing triazine thiol derivative (the result of the above-mentioned alkoxysilane part being chemically bonded to the metal is the result of the alkoxysilane-containing triazine thiol). The product can be chemically bonded via a product generated from the derivative, thereby making it possible to obtain a strong bonding force.

  Usually, the bond between the alkoxysilane group of the alkoxysilane-containing triazine thiol derivative and the metal is prepared by preparing a solution of the alkoxysilane-containing triazine thiol derivative, and immersing the metal in this solution to form a hydroxyl group (OH group) on the metal surface. This is performed by reacting an alkoxysilane group. For this reason, a method of removing an oxide film on a metal surface by plasma treatment and introducing a hydroxyl group (OH group) on the metal surface is generally used.

  However, since iron has a strong binding force with oxygen, and the oxide film formed on the surface of the iron alloy is dense and strong, the OH group is not sufficiently introduced, and the iron alloy and the alkoxysilane group It can be presumed that a sufficient number of bonds (density) cannot be obtained. In addition, simply removing the iron oxide film results in the formation of a new oxide film immediately after iron is combined with oxygen, so that a high bonding strength cannot be obtained.

Therefore, the present inventors surface-treat the iron alloy substrate to react with and bond to the alkoxysilane group on the metal surface, hydroxide, carboxylate, phosphate, sulfate, thiosulfate, The present application in which after forming a metal compound film containing at least one of chloride and perchloride, the iron alloy substrate and the resin disposed on the surface thereof are strongly bonded using alkoxysilane-containing triazine thiol. It came to the invention of description.
Details of the present invention will be described below.

FIG. 1 is a cross-sectional view schematically showing a part of an iron alloy article according to the present invention, the whole of which is represented by 100. As shown in FIG. An iron alloy substrate 1 made of iron or an iron alloy and a resin layer 4 are bonded via a metal compound film 2 and a dehydrated silanol-containing triazine thiol derivative coating 3 which will be described in detail later.
FIG. 2 shows a cross section of a conventional iron alloy article 200 in which the iron alloy substrate 1 and the resin layer 4 are joined using the dehydrated silanol-containing triazine thiol derivative 3. The conventional iron alloy article 200 does not have the metal compound film 2.

The metal compound film 2 that is a feature of the iron alloy article 100 according to the present invention is at least selected from the group consisting of hydroxide, carboxylate, phosphate, sulfate, thiosulfate, chloride, and perchloride. One.
A method of manufacturing the iron alloy article 100 of the present invention in which the iron alloy substrate 1 and the resin 4 are strongly bonded by using the metal compound film 2 will be described in detail below.

1. Pretreatment It is preferable to perform a degreasing treatment as a pretreatment before performing a treatment (metal compound treatment) for forming a metal compound film, which will be described in detail later.

  The degreasing treatment may be a method usually used for degreasing of an iron alloy base molded article, for example, degreasing using a strong alkali such as sodium hydroxide. Preferred degreasing conditions are, for example, degreasing in sodium hydroxide at a concentration of 10 to 100 g / L and a temperature of 50C to 90C. More preferable conditions are that after preliminary degreasing in sodium hydroxide at a concentration of 10 to 100 g / L (most preferably 10 to 20 g / L) and a temperature of 50 ° C. to 90 ° C., a concentration of 10 to 100 g / L ( Most preferably, degreasing is performed in sodium hydroxide at a temperature of 50 ° C. to 90 ° C.

  In addition, sodium salts such as sodium carbonate, sodium bicarbonate, borax, silicates such as sodium orthosilicate, sodium silicate, primary sodium phosphate, secondary sodium phosphate, tertiary sodium phosphate Degreasing may be performed using various phosphates such as sodium phosphate, sodium pyrophosphate, and sodium hexametaphosphate.

  The iron alloy substrate 1 is made of iron or an iron alloy, and any iron alloy used in industry can be used as the iron alloy. Examples of preferred iron alloys are carbon steel, alloy steel, nickel chromium steel (nickel chromium stainless steel), nickel chromium molybdenum steel, chromium steel, chromium molybdenum steel, manganese steel.

  And the shape may be any shape including a plate shape such as a rolled plate, a tubular shape such as a pipe, and a cylindrical shape such as a wire.

2. Metal compound treatment After the degreasing treatment (pretreatment), the surface of the iron alloy substrate 1 is subjected to the following metal compound treatment (also referred to as “compound treatment”) to produce hydroxide, carboxylate, phosphate, sulfate. Then, a metal compound film 2 (also referred to as “compound film”) containing at least one of thiosulfate, chloride, and perchloride is formed.
The metal compound treatment is carried out using at least one of the following acids or compounds.

  The “metal” in the “metal compound coating” shown in this specification refers to the metal contained in the iron alloy substrate 1 and the metal contained in the solution (metal compound treatment liquid) used in the metal compound treatment shown in detail below. Means at least one of

(1) Carboxylic acid, carboxylate salt An iron alloy substrate 1 is treated with a metal compound using an aqueous carboxylic acid solution such as tannic acid. As a result, a metal compound film mainly composed of iron salt and / or metal salt of carboxylic acid and / or hydroxide is formed on the surface of the iron alloy substrate 1.

  Alternatively, the metal compound treatment may be performed using an aqueous solution of an alkali metal salt such as a sodium salt or potassium salt of a carboxylic acid such as lauric acid, palmitic acid, or stearic acid. In this case, a metal compound film 2 mainly composed of alkali metal salts of these carboxylic acids and hydroxides is formed on the surface of the iron alloy substrate 1. The metal compound film 2 may contain the iron salt and / or metal salt of the carboxylic acid.

  The metal compound treatment may be performed using an aqueous solution of a metal salt of formic acid, acetic acid, oxalic acid, or succinic acid. In this case, a metal compound film 2 mainly composed of a metal salt of these carboxylic acids and / or a hydroxide is formed on the surface of the iron alloy substrate 1. The metal compound film 2 may contain the iron salt of the carboxylic acid. For example, when the metal compound treatment is performed using an aqueous metal oxalate salt solution, the aqueous solution preferably has a concentration of 0.5 to 100 g / L and a temperature of 30 to 70 ° C.

(2) Phosphoric acid, phosphate Phosphoric acid, metal hydrogen phosphate such as zinc hydrogen phosphate, manganese hydrogen phosphate, calcium hydrogen phosphate, metal dihydrogen phosphate such as calcium dihydrogen phosphate salts and, for example zinc phosphate, manganese phosphate, calcium phosphate, sodium calcium phosphate, _-H 2 _PO 4, such as phosphoric acid metal salts such as zirconium phosphate, phosphoric acid and phosphate containing -HPO ₄ or -PO ₄ The metal compound treatment is performed using a salt solution. The phosphoric acid referred to in this specification is phosphoric acid in a broad sense including orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and the like, and phosphate refers to orthophosphoric acid, metaphosphoric acid, pyrolinic acid. It is a concept including a compound of phosphoric acid in a broad sense such as acid, triphosphoric acid, and tetraphosphoric acid.

  By using phosphoric acid, the metal compound film 2 mainly composed of iron phosphate and / or metal phosphate and / or hydroxide is formed on the surface of the iron alloy substrate 1.

  Meanwhile, zinc phosphate, zinc hydrogen phosphate, manganese phosphate, manganese hydrogen phosphate, metal hydrogen phosphate, metal dihydrogen phosphate, metal phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium phosphate The surface of the iron alloy substrate 1 is subjected to a metal compound treatment using an aqueous solution of a phosphate (metal salt of phosphoric acid) such as sodium calcium phosphate and zirconium phosphate. It is possible to form a metal compound film 2 containing an object as a main component. These metal salt film 2 of phosphate and / or hydroxide may contain iron phosphate and / or metal phosphate. Further, for example, a plurality of phosphates other than iron phosphate and metal phosphate may be included by performing a metal compound treatment in a solution in which different types of metal phosphates are mixed.

  For example, when the metal compound treatment is performed using an aqueous solution of zirconium phosphate, the aqueous solution preferably has a concentration of 1 to 100 g / L and a temperature of 20 to 90 ° C. Other than this, phosphoric acid, zinc phosphate, zinc hydrogen phosphate, manganese phosphate, manganese hydrogen phosphate, hydrogen phosphate metal salt, dihydrogen phosphate metal salt, metal phosphate phosphate, calcium hydrogen phosphate, phosphorus When using an aqueous solution of phosphoric acid and phosphate such as calcium dihydrogen phosphate, calcium phosphate, and sodium calcium phosphate, the aqueous solution preferably has a concentration of 5 to 30 g / L and a temperature of 20 to 90 ° C. Is more preferably 25 ° C to 75 ° C.

(3) Sulfuric acid, sulfate salt Metal compound treatment is performed using sulfuric acid or an aqueous metal salt solution of sulfuric acid such as sodium sulfate, manganese sulfate, calcium sulfate, titanyl sulfate, zirconium sulfate, potassium sulfate, sodium sulfate. When sulfuric acid is used, a metal compound film 2 mainly composed of iron sulfate, metal sulfate or hydroxide, or a mixture thereof is formed on the surface of the iron alloy substrate 1. On the other hand, when an aqueous metal salt solution of sulfuric acid such as sodium sulfate, manganese sulfate, calcium sulfate, titanyl sulfate, zirconium sulfate, potassium sulfate, sodium sulfate is used, a metal compound mainly composed of these metal salts and / or hydroxides A film 2 is formed. The obtained metal compound film 2 may contain iron sulfate and / or a metal sulfate.
For example, when the metal compound treatment is performed using an aqueous solution of potassium sulfate metal salt, the aqueous solution preferably has a concentration of 0.5 to 30 g / L and a temperature of 30 to 60 ° C.

(4) Thiosulfate The metal compound treatment is performed using an aqueous solution of thiosulfate such as sodium thiosulfate and calcium thiosulfate. A metal compound film 2 mainly composed of these thiosulfates and / or hydroxides is formed on the surface of the iron substrate 1. The obtained metal compound film 2 may contain iron thiosulfate and / or metal thiosulfate.
For example, when the metal compound treatment is performed using an aqueous solution of calcium thiosulfate, the aqueous solution preferably has a concentration of 20 to 50 g / L and a temperature of 40 to 60 ° C.

(5) Hydrochloric acid, chloride Metal compound treatment is performed using hydrochloric acid or an aqueous metal salt solution of hydrochloric acid such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, iron chloride, and aluminum chloride. When hydrochloric acid is used, a metal compound film 2 mainly composed of iron chloride, metal chloride or hydroxide, or a mixture thereof is formed on the surface of the iron alloy substrate 1. On the other hand, when an aqueous metal salt solution such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, iron chloride, or aluminum chloride is used, a metal compound film 2 mainly composed of these metal salts and / or hydroxides is formed. The The obtained metal compound film 2 may contain iron chloride and / or metal chloride.
For example, when the metal compound treatment is performed using an aqueous solution of potassium chloride metal salt, the aqueous solution preferably has a concentration of 5 to 100 g / L and a temperature of 50 to 90 ° C.

(6) Perchloric acid, perchlorate Perchloric acid or sodium perchlorate, potassium perchlorate, calcium perchlorate, ammonium perchlorate, iron perchlorate, copper perchlorate, nickel perchlorate The metal compound treatment is performed using an aqueous metal salt solution of perchloric acid. When perchloric acid is used, a metal compound film 2 mainly composed of iron chloride, metal chloride or hydroxide, or a mixture thereof is formed on the surface of the iron alloy substrate 1. On the other hand, when using an aqueous metal salt solution of perchloric acid such as sodium perchlorate, potassium perchlorate, calcium perchlorate, ammonium perchlorate, iron perchlorate, copper perchlorate, nickel perchlorate, A metal compound film 2 mainly composed of these metal salts and / or hydroxides is formed. The obtained metal compound film 2 may contain iron chloride and / or metal chloride.
For example, when the metal compound treatment is performed using iron perchlorate, the aqueous solution preferably has a concentration of 1 to 50 g / L and a temperature of 30 to 60 ° C.

  Among the metal compound treatments described above, a method using a sulfuric acid compound (or sulfuric acid) or a thiosulfuric acid compound is preferable, and a method using a sulfuric acid compound (or sulfuric acid) is more preferable.

In the method using phosphoric acid and phosphate, it is possible to form a relatively uniform metal compound film 2 having a thickness of preferably 0.05 to 5 μm, more preferably 0.05 to 2 μm. is there.
Therefore, the silanol and metal compound film component produced by the alkoxysilane-containing triazine thiol derivative penetrating into the metal compound film 2 and reacting with the metal compound film 2 are increased, and the alkoxysilane of the triazine thiol derivative is hydrolyzed. The phosphoric acid group and / or hydroxyl group of the compound undergoes a dehydration reaction by heat treatment and is chemically bonded. In this way, a stronger bond can be obtained between the resulting dehydrated silanol-containing triazine thiol derivative coating 3 and the metal compound film 2.

  Further, when the resin 4 is cooled and contracts after bonding, the relatively thick metal compound film 2 disperses and absorbs stress generated between the resin 4 and the metal compound film 2, and the resin 4 is peeled off and the metal compound film. 2 has the effect of preventing the occurrence of cracks. The concentration and temperature of phosphoric acid or phosphate are preferably 5 to 50 g / L, and the solution temperature is preferably 30 to 60 ° C. Within this range, it is possible to obtain a dense metal compound film 2 in a relatively short time.

  The metal compound treatment using the above solution not only immerses the whole or part of the iron alloy substrate 1 in the solution (metal compound treatment solution) but also all or part of the surface of the iron alloy substrate 2. Coating the solution by spraying, coating, etc., or contacting with the solution.

  Therefore, as is apparent from the above, the metal compound film 2 is not necessarily formed on the entire surface of the iron alloy substrate 2, and may be formed only on necessary portions as appropriate.

Needless to say, the above metal compound treatments can be combined.
That is, you may perform a metal compound process using the solution which mixed the solution (metal compound process liquid) used for the several metal compound process mentioned above. Moreover, after performing a metal compound process using one kind of the solution (metal compound process liquid) used for the metal compound process mentioned above, a metal compound process is further performed using another kind of metal compound process liquid. Also good.

The metal compound coating 2 obtained by the above-described metal compound treatment is often roughened. That is, the surface roughness of the metal compound coating 2 is often rougher than the surface roughness of the iron alloy substrate 1 before the metal compound treatment.
For example, the arithmetic average roughness Ra is obtained by performing the above-described metal compound treatment on the surface of the iron alloy substrate 1 having an arithmetic average roughness Ra of 0.09 μm or less as defined in Japanese Industrial Standard (JIS B0601: 2001). A metal compound film 2 having a thickness of 0.10 μm or more can be formed.
The surface roughening of the metal compound coating 2 can increase the contact area between the dehydrated silanol-containing triazine thiol derivative coating 3 formed on the metal compound coating 2 and the metal compound coating 2, and thus contributes to an improvement in bonding strength. .

3. Coating of Alkoxysilane-Containing Triazine Thiol Derivative After forming the metal compound film 2 on the surface of the iron alloy substrate 1 by the method described above, the metal compound film 2 is coated with the alkoxysilane-containing triazine thiol derivative.
The alkoxysilane-containing triazine thiol derivative used may be a known one such as an alkoxysilane-containing triazine thiol metal salt.
That is, it is represented by the general formula shown in the following (Formula 1) or (Formula 2).

R ¹ in the formula is, for example, any one of H—, CH ₃ —, C ₂ H ₅ —, CH ₂ ═CHCH ₂ —, C ₄ H ₉ —, C ₆ H ₅ —, C ₆ H ₁₃ —. is there. R ² is, for example, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ SCH ₂ CH ₂ —, —CH. ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ —. R ³ is, for example, — (CH ₂ CH ₂ ) ₂ CHOCONHCH ₂ CH ₂ CH ₂ — or — (CH ₂ CH ₂ ) ₂ N—CH ₂ CH ₂ CH ₂ —, in which case N and R ³ is a ring structure.

X in the formula _{is, CH 3 -, C 2 H} 5 -, n-C 3 H 7 -, i-C 3 H 7 -, n-C 4 H 9 -, i-C 4 H 9 -, t- One of C ₄ H ₉ —. Y _{is, CH 3 O-, C 2 H} 5 O-, n-C 3 H 7 O-, i-C 3 H 7 O-, n-C 4 H 9 O-, i-C 4 H 9 O- a _{t-C 4 H} 9 O- and alkoxy groups. N in a formula is either 1, 2, or 3 numbers. M is an alkali metal, preferably Li, Na, K or Ce.

  When the metal compound film 2 is coated, a solution of an alkoxysilane-containing triazine thiol derivative is then prepared. The solvent to be used is not particularly limited as long as the alkoxysilane-containing triazine dithiol derivative can be dissolved, and water and alcohol solvents correspond to this. For example, water, methanol, ethanol, propanol, carbitol, ethylene glycol, polyethylene glycol, and a mixed solvent thereof can be used. A preferable concentration of the alkoxysilane-containing triazine dithiol derivative is 0.001 g to 20 g / L, and a more preferable concentration is 0.01 g to 10 g / L.

  In the obtained alkoxysilane-containing triazine dithiol derivative solution, the iron alloy substrate 1 provided with the metal compound film 2 is immersed. The preferable temperature range of a solution and the more preferable temperature range are 0 degreeC-100 degreeC, and 20 degreeC-80 degreeC, respectively. On the other hand, the immersion time is preferably 1 minute to 200 minutes, more preferably 3 minutes to 120 minutes.

  By this immersion, the alkoxysilane portion of the alkoxysilane-containing triazine thiol derivative becomes silanol, and by the heat treatment, the hydroxide, carboxylate, phosphate, sulfate, thiosulfate, chloride contained in the metal compound film 2 described above. Since it is dehydrated with at least one of the product and perchloride, the alkoxysilane-containing triazine thiol derivative after immersion becomes a silanol-containing triazine thiol derivative, which forms a hydrogen-bonded loose bond with the metal compound film 2 to form a chemical bond. A binding force can be obtained.

  Therefore, an iron alloy member used for joining a resin to the surface, which is composed of the iron alloy substrate 1, the metal compound film 2, and the silanol-containing triazine thiol derivative coating, can thus be obtained.

  Then, this iron alloy member is heated to 100 ° C. to 450 ° C. for the purpose of drying and dehydration reaction promoting heat treatment. This heating causes a dehydration bond reaction to occur in the silanol portion of the silanol-containing triazine thiol derivative. Therefore, the silanol-containing triazine thiol derivative is changed into a dehydrated silanol-containing triazine thiol derivative and chemically bonded to the metal compound film 2. To do.

  Therefore, an iron alloy member used for bonding a resin to the surface, which is composed of the iron alloy substrate 1, the metal compound film 2, and the dehydrated silanol-containing triazine thiol derivative coating 3, can be obtained.

  Next, in order to strengthen the bonding force between the dehydrated silanol-containing triazine thiol derivative and the resin, the dehydrated silanol-containing triazine thiol derivative formed on the metal compound film 2 is appropriately used as a bonding aid as necessary. For example, compounds having binding properties by radical reaction such as N, N′-m-phenylene dimaleimide, which is a dimaleimide, and N, N′-hexameethylene dimaleimide, and diclemyl peroxide, benzoyl peroxide, etc. Immerse in a solution containing peroxide or other radical initiator. After immersion, the iron alloy member is dried and heat-treated at 30 ° C. to 270 ° C. for 1 minute to 600 minutes.

As a result, the dehydrated silanol-containing triazine thiol derivative removes the metal ion of the triazine thiol metal salt (triazine thiol derivative) portion, and the sulfur becomes a mercapto group, and this mercapto group becomes N, N′-m-phenylenedimaleimide. It reacts with one of the two double bonds of maleic acid to form a dehydrated silanol-containing triazine thiol derivative bonded with N, N′-m-phenylene dimaleimide.
The radical initiator has a function of generating a radical by decomposition by heat such as heating performed when molding a resin, opening the other bond of the two double bonds by the maleic acid, and reacting and bonding with the resin.

  Furthermore, if necessary, a solution in which a radical initiator such as a peroxide or a redox catalyst is dissolved in an organic solvent such as benzene or ethanol is attached to the surface of the iron alloy member by spraying by dipping or spraying. Air dry.

  The radical initiator generates radicals by thermal decomposition such as heating performed when molding the resin, opens the other bond of the two double bonds by the maleic acid, or forms a metal salt part of the triazine thiol derivative. It works to react and bond with the resin.

4). Bonding with Resin An iron alloy member having the metal compound film 2 and the dehydrated silanol-containing triazine thiol derivative layer 3 on the surface of the iron metal substrate 1 and the resin 4 are bonded (composite integrated) to obtain an iron article 100. The resin 4 is disposed so as to be in contact with the dehydrated silanol-containing triazine thiol derivative layer 3 in a heated state. As a result, the resin 4 and the triazine thiol derivative part of the dehydrated silanol-containing triazine thiol derivative 3 (triazine thiol metal salt part or triazine thiol derivative combined with bismaleimides) react with the radical of the radical initiator as a chemical, Create a bond.
The resin may be disposed only on a part of the dehydrated silanol-containing triazine thiol derivative coating 3.

  As a method of arranging the heated resin 4 on the dehydrated silanol-containing triazine thiol derivative coating 3, for example, an iron alloy member (including the metal substrate 1, the metal compound film 2, and the dehydrated silanol-containing triazine thiol derivative coating 3) is used as a mold. When a molten resin is injected into a mold to obtain an insert molded article or an outsert molded article, the radical initiator is decomposed by the heat of the mold and the resin, and the triazine thiol derivative coating and the resin are reacted by a radical reaction. Is an injection molding method in which the iron alloy member and the resin 4 are bonded together, or after the resin molding, the injection molded product is heated in an oven or a hot plate to decompose the radical initiator and chemically bond by radical reaction. Thus, a welding method for joining the iron alloy member and the resin can be used.

  In the case of injection molding, the mold temperature is 20 to 220 ° C., 5 seconds to 10 minutes, and in the case of the welding method, the oven or hot plate temperature is maintained at 30 to 430 ° C. for 1 minute to 10 hours. The temperature needs to be equal to or higher than the decomposition temperature of the radical initiator, and the holding time needs a sufficient time for the radical to form a chemical bond between the triazine thiol derivative and the resin.

  The joining of the iron alloy member and the resin is not limited to the above-described injection molding and the welding method for heating the injection-molded product, and any joining technique for industrially used iron alloy and resin is used. be able to. A preferred example of such a joining method is hot plate welding. Hot plate welding is a method in which a resin is brought into contact with a heat source such as a hot plate and melted, and the iron alloy member is pressed and joined before the melted resin cools and solidifies.

  As the resin to be joined, any industrially usable resin can be used, but a resin having an element that reacts with a radical or a functional group is preferable. Examples of such preferred resins are phenol resin, hydroquinone resin, cresol resin, polyvinyl phenol resin, resorcin resin, melamine resin, glyphtal resin, epoxy resin, modified epoxy resin, polyvinyl formal resin, polyhydroxymethyl methacrylate and its co-polymer. Polymer, polyhydroxyethyl acrylate and copolymer, acrylic resin, polyvinyl alcohol and copolymer, polyvinyl acetate, polyethylene terephthalate resin, polyimide resin, polyetherimide resin, polyketoneimide resin, polybutylene terephthalate resin, unsaturated Polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, polystyrene resin, ABS resin, polycarbonate resin (PC resin), 6-nylon resin , 66-nylon resin, 610-nylon resin, aromatic polyamide resin, urea resin, styrene elastomer resin, olefin elastomer resin, vinyl chloride elastomer resin, urethane elastomer resin, ester elastomer resin, amide elastomer resin, and A composite resin in which two or more selected from these resins are combined, and a reinforced resin in which these resins are reinforced with glass fibers, carbon fibers, ceramics, or the like.

  As described above, it is possible to manufacture the iron alloy article 100 in which the iron alloy substrate 1 and the resin 4 are joined through the metal compound film 2 and the dehydrated silanol-containing triazine thiol derivative coating 3.

  In addition to the advantage of high bonding strength between the iron alloy substrate and the resin, the iron alloy article obtained by this method does not require any special machining on the surface of the iron article. Since the resin can be joined without using a relaxation elastic resin or the like, there are advantages in that the number of processing steps is small, the joint is finished cleanly, and can be finished with high dimensional accuracy.

  Furthermore, by covering a portion of the iron base, which is difficult to be molded, with poor molding accuracy with a resin, the article is finished with the resin molding accuracy and the yield of the product can be increased.

(1) Pretreatment A plate of SUS304 (18Cr-8Ni stainless steel, surface finish No. 2B defined by Japanese Industrial Standard) having a length of 80 mm, a width of 20 mm, and a thickness of 1.5 mm, and a length of 80 mm and a width of 20 mm A cold rolled steel sheet as defined in SPCC (Japanese Industrial Standard, JIS G 3141: 2005) having a thickness of 1.2 mm was pretreated.

  The pretreatment (degreasing treatment) is carried out by preliminarily degreasing all the samples of Examples and Comparative Examples in an aqueous sodium hydroxide solution having a concentration of 15.0 g / L and a temperature of 60 ° C. After degreasing in a 70 ° C. aqueous sodium hydroxide solution for 60 seconds, washing with water was performed for 60 seconds, followed by drying in an oven at 80 ° C. for 30 minutes.

(2) Metal compound treatment The following metal compound treatment was performed on the SUS304 plate (iron alloy substrate) subjected to the degreasing treatment in order to obtain the samples of Examples 1-1 to 1-3.

  The sample of Example 1-1 was etched for 300 seconds in a sulfuric acid aqueous solution (95% or more of components other than water was sulfuric acid) at a temperature of 60 ° C. and a concentration of 40 to 50 g / L, and then washed with hot water (60 ° C.) and water. For 60 seconds, and then immersed in a sodium hydroxide solution having a concentration of 60 g / L and a temperature of 70 ° C. for 180 seconds to form a metal compound film mainly composed of iron, chromium, nickel, manganese hydroxide and sulfate. Was obtained on the surface of the iron alloy plate.

  In the sample of Example 1-2, the strong acid (sulfuric acid) etching of Example 1-1 was changed to 600 seconds.

  In the sample of Example 1-3, it was immersed in an aqueous manganese phosphate solution having a concentration of 7.5 to 10.0 g / L and a temperature of 35 ° C. for 30 seconds, and manganese phosphate was the main component, and iron, chromium, nickel, manganese A metal compound film containing a hydroxide was obtained on the surface of a SUS304 plate.

Further, the following pretreatment was performed on the SUS304 plate that had been pretreated to obtain the samples of Examples 2-1 to 2-24, and the above treatment was performed to obtain Examples 2-25 to 2-46. SPCC (cold rolled steel sheet) was subjected to the following metal compound treatment.
Moreover, the detail about the comparative example samples 2-1 to 2-4 which do not perform a metal compound process is also shown below.
Table 1 shows the production conditions of Examples 2-1 to 2-46 and Comparative Examples 2-1 to 2-8.

Moreover, about the sample of Examples 2-1 to 2-46, surface roughness Ra (arithmetic mean roughness Ra prescribed | regulated to JISB0601: 2001) was measured after the metal compound process. On the other hand, for Comparative Examples 2-1 to 2-8 in which the metal compound treatment was not performed, the surface roughness Ra was measured after the above degreasing treatment (pretreatment).
The surface roughness Ra was measured using a laser microscope VK-8710 manufactured by Keyence Corporation. For comparison, the surface roughness of untreated samples (samples not subjected to degreasing treatment) was also measured.
Table 1 shows the measurement results of the surface roughness Ra. The surface roughness Ra of the untreated sample was 0.08 μm for SUS304, and 0.34 μm for SPCC (cold rolled steel sheet).

  The samples of Examples 2-1 to 2-8 were etched for 300 seconds in a sulfuric acid aqueous solution (95% or more of components other than water were sulfuric acid) at a temperature of 60 ° C. and a concentration of 40 to 50 g / L, and then washed with hot water (60 ℃) and water washing for 60 seconds each. By this treatment, a metal compound film mainly composed of iron, chromium, nickel, manganese hydroxide and sulfate was obtained on the surfaces of the samples of Examples 2-1 to 2-8 on the surface of the iron alloy plate. Ra after the metal compound treatment was 0.15 to 0.23 μm, which was increased by 0.06 to 0.14 μm compared to the untreated sample.

  Samples of Examples 2-9 to 2-12 were mixed acid aqueous solutions in which oxalic acid having a concentration of 90 to 120 g / L was added to sulfuric acid having a concentration of 90 to 120 g / L (95% or more of components other than water were sulfuric acid and Acid) for 600 seconds at a temperature of 60 ° C., then washed with water for 60 seconds, immersed in diluted nitric acid at a concentration of 20 g / L and room temperature for 600 seconds, and then washed with water for 60 seconds. By this treatment, metal compound films mainly composed of hydroxides of iron, chromium, nickel, manganese, sulfates, oxalates, and nitrates were obtained on the surfaces of the samples of Examples 2-9 to 2-12. Ra after the metal compound treatment was 0.29 to 0.38 μm, which was 0.21 to 0.30 μm higher than that of the untreated sample.

  The samples of Examples 2-13 to 2-16 were etched for 300 seconds in an aqueous sulfuric acid solution having a temperature of 60 ° C. and a concentration of 40 to 50 g / L (95% or more of components other than water were sulfuric acid), and washed with hot water (60 ° C. ) And water washing for 60 seconds each, followed by immersion for 180 seconds in a phosphoric acid aqueous solution (90% or more of components other than water are phosphoric acid) at a temperature of 40 ° C. and a concentration of 10 to 30 g / L, followed by water washing for 60 seconds. By this treatment, a metal compound film mainly composed of a metal salt of phosphoric acid and a hydroxide was obtained on the sample surfaces of Examples 2-13 to 2-16. Ra after the metal compound treatment was 0.17 to 0.20 μm, which was increased by 0.09 to 0.12 μm compared to the untreated sample.

  The samples of Examples 2-17 to 2-20 were etched for 300 seconds in an aqueous sulfuric acid solution having a temperature of 60 ° C. and a concentration of 40 to 50 g / L (95% or more of components other than water were sulfuric acid), and then washed with hot water (60 C.) and water washing for 60 seconds each, and then immersed in an aqueous hydrochloric acid solution at a temperature of 60 ° C. and a concentration of 90 to 120 g / L (95% or more of components other than water is hydrochloric acid) for 300 seconds and washed with water for 60 seconds. By this treatment, a metal compound film mainly containing iron, chromium, nickel, manganese hydroxide, sulfate, and chloride was obtained on the surface of the samples of Examples 2-17 to 2-20. Ra after the metal compound treatment was 0.18 to 0.19 μm, which was 0.10 to 0.11 μm higher than that of the untreated sample.

  The samples of Examples 2-21 to 2-24 were etched for 300 seconds in a sulfuric acid aqueous solution (95% or more of components other than water were sulfuric acid) at a temperature of 60 ° C. and a concentration of 40 to 50 g / L, and then washed with hot water (60 C.) and water washing for 60 seconds each, followed by immersion for 300 seconds in a nitric acid aqueous solution having a temperature of 60.degree. By this treatment, a metal compound film containing iron, chromium, nickel, manganese hydroxide, sulfate, and nitrate as main components was obtained on the sample surfaces of Examples 2-21 to 2-24. Ra after the metal compound treatment was 0.16 to 0.17 μm, an increase of 0.08 to 0.09 μm compared to the untreated sample.

  The samples of Examples 2-25 to 2-33 were etched for 300 seconds in an aqueous phosphoric acid solution having a temperature of 60 ° C. and a concentration of 30 to 50 g / L (90% or more of components other than water were phosphoric acid), and then washed with hot water (60 ° C.) and water washing were performed for 60 seconds each. By this treatment, a metal compound film mainly composed of a metal salt of phosphoric acid and a hydroxide was obtained on the sample surfaces of Examples 2-25 to 2-33. Ra after the metal compound treatment was 0.51 to 0.61 μm and increased by 0.17 to 0.27 μm compared to the untreated sample.

  The samples of Examples 2-34 to 2-36 were etched for 300 seconds in an aqueous hydrochloric acid solution having a temperature of 60 ° C. and a concentration of 80 to 100 g / L (95% or more of components other than water were hydrochloric acid), and then washed with hot water (60 ° C) and water washing for 60 seconds each. By this treatment, metal compound films mainly composed of iron, manganese chloride and hydroxide were obtained on the sample surfaces of Examples 2-34 to 2-36. Ra after the metal compound treatment was 0.58 to 0.67 μm, which was 0.24 to 0.33 μm higher than that of the untreated sample.

  The samples of Examples 2-37 to 2-40 were etched for 300 seconds in a sulfuric acid aqueous solution (95% or more of components other than water were sulfuric acid) at a temperature of 60 ° C. and a concentration of 40 to 50 g / L, and then washed with hot water (60 ℃) and water washing for 60 seconds each, then immersed in a phosphoric acid aqueous solution (90% or more of components other than water is phosphoric acid) at a temperature of 40 ° C and a concentration of 10 to 30 g / L for 180 seconds and washed with water for 60 seconds. . By this treatment, a metal compound film containing phosphoric acid metal salt and hydroxide as main components was obtained on the sample surfaces of Examples 2-37 to 2-40. Ra after the metal compound treatment was 0.77 to 0.86 μm, which was increased by 0.34 to 0.52 μm compared to the untreated sample.

  The samples of Examples 2-41 to 2-43 were etched for 300 seconds in an aqueous nitric acid solution having a temperature of 60 ° C. and a concentration of 150 to 200 g / L (95% or more of components other than water were nitric acid), and then washed with water for 60 seconds. . By this treatment, a metal compound film mainly composed of iron, manganese nitrate and hydroxide was obtained on the sample surfaces of Examples 2-41 to 2-43. Ra after the metal compound treatment was 2.07 to 2.30 μm, and increased by 1.73 to 1.96 μm as compared with the untreated sample.

  The samples of Examples 2-44 to 2-46 were immersed in a colloidal solution of zinc phosphate fine particles having a temperature of 30 ° C. and a concentration of 0.5 to 0.75 g / L for 300 seconds and washed with water for 60 seconds. By this treatment, zinc phosphate fine particles were adhered to the sample surfaces of Examples 2-44 to 2-46. The zinc phosphate fine particles are adhered to the sample surface with a micron-level gap therebetween, and the surface of the sample is not completely covered with the zinc phosphate fine particles (that is, the metal compound film). Ra after the metal compound treatment was 0.30 to 0.37 μm, which was comparable to that of the untreated sample.

  As a comparative example, the SUS304 plate subjected only to the above-described degreasing treatment is referred to as Comparative Example 1-1, and instead of performing the metal compound treatment on the SUS304 plate subjected to the degreasing treatment used in Example 1-2, an aminosilane-based silane coupling agent is used. It was made to adhere and it was set as Comparative Example 1-2. The adhesion of the silane coupling agent was carried out by preparing a 1% aqueous solution of KBM-603 (N-2- (aminoethyl) -3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. After being immersed in this aqueous solution for 60 seconds, it was dried in an oven at 110 ° C. for 10 minutes.

Further, Comparative Example 2 shown in Table 2 using SUS304 (Comparative Examples 2-1, 2-5 and 2-7) and SPCC plates (Comparative Examples 2-2 to 2-4, 2-6 and 2-8), respectively. Samples of -1 to 2-8 were produced.
The samples of Comparative Examples 2-1 to 2-8 were all subjected to the degreasing treatment (pretreatment) among the above pretreatments, but were not subjected to the metal compound treatment.

In Comparative Examples 2-1, 2-2, 2-5, and 2-6, only the degreasing treatment was performed.
The sample of Comparative Example 2-3 was subjected to # 60 paper polishing before the degreasing treatment in addition to the degreasing treatment.
In addition to the degreasing treatment, the sample of Comparative Example 2-4 was blasted so that the surface roughness Ra was 6.0 μm or more before the degreasing treatment.

  Further, in Comparative Examples 2-7 and 2-8, the sample subjected to the degreasing treatment in the pretreatment was treated with an aminosilane-based silane coupling agent (KBM-603 (N-2- (amino) manufactured by Shin-Etsu Chemical Co., Ltd.). It was prepared by immersing in a 1% aqueous solution of ethyl) -3-aminopropyltrimethoxysilane)) at room temperature for 60 seconds and then drying in an oven at 110 ° C. for 10 minutes. In Comparative Example 2-3, Ra increased by 0.11 μm compared to the untreated sample at 0.45 μm, and in Comparative Example 2-4 increased by 5.82 μm compared to the untreated sample at 6.16 μm. did. The Ra of the other comparative samples was about the same as the untreated sample.

(3) Coating of alkoxysilane-containing triazine thiol derivative Next, samples of Examples 1-1 to 1-3, Comparative Examples 1-1, 1-2, and Examples 2-1 to 2-46 were used as alkoxysilane-containing triazine thiol derivatives. It was immersed in the solution.
The alkoxysilane-containing triazine thiol derivative used was triethoxysilylpropylaminotriazine thiol monosodium, dissolved in a solvent of ethanol 95: water 5 (volume ratio) so that the concentration was 0.7 g / L, and the solution was dissolved. Obtained. This triethoxysilylpropylaminotriazine thiol monosodium solution was immersed for 30 minutes at room temperature.

  Thereafter, these samples were heat-treated in an oven at 160 ° C. for 10 minutes to complete the reaction and dry. Then, an acetone solution containing N, N′-m-phenylene dimaleimide (N, N′-1,3-phenylene dimaleimide) having a concentration of 1.0 g / L and dicumyl peroxide having a concentration of 2 g / L was added to room temperature. And then heat-treated in an oven at 150 ° C. for 10 minutes. Thereafter, an ethanol solution of dicumyl peroxide having a concentration of 2 g / L was sprayed on the entire surface of the sample at room temperature and air-dried.

(4) Joining with resin Next, the samples of Examples 1-1 to 1-3, Comparative Example 1-1, and Comparative Example 1-2 were placed in a mold heated to 120 ° C., and one part of the surface was An ABS resin sample manufactured by Asahi Kasei Chemicals Corporation (Stylac (R) —ABS General Purpose 026) was injection molded at 220 ° C. so as to be bonded to the resin to obtain an iron article sample.
The resin is molded in a mold so as to be a plate having a length of 80 mm, a width of 20 mm, and a thickness of 3 mm. It arrange | positions on the terminal part of an alloy plate sample, and contacts the part of length 12mm and width 20mm, and this part has joined. The iron alloy article obtained after the mold was cooled to 80 ° C. or lower was taken out.

  Further, Examples 2-1 to 2-4, 2-9 to 2-28, 2-34 to 2-45, and Comparative Examples 2-1 to 2-4, 2-7 and 2- 8 samples were placed in a mold heated to 200 ° C. (the same mold as in Examples 1 to 3), and 1 part of the surface (similar to Examples 1 to 3, a part having a length of 12 mm and a width of 20 mm) ) Is bonded to a resin (a plate having a length of 80 mm, a width of 20 mm, and a thickness of 3 mm as in Examples 1 to 3), and an iron alloy is formed by injection molding using the resins shown in Table 2 under the conditions shown below. A sample of the article was obtained.

  In the samples of Examples 2-1, 2-9, 2-13, 2-17, 2-21, 2-25, 2-34, 2-37, 2-41 and Comparative Examples 2-1, 2-7 Injection molding was performed at a resin temperature of 220 ° C. using ABS resin (Stylac (R) —ABS General Purpose 026) manufactured by Asahi Kasei Chemicals Corporation.

  In the samples of Examples 2-2, 2-10, 2-14, 2-18, 2-22, 2-26 and 2-38, PC / ABS resin (Iupilon MB2215R) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used. Then, injection molding was performed at a resin temperature of 270 ° C.

  Examples 2-3, 2-11, 2-15, 2-19, 2-23, 2-27, 2-35, 2-39, 2-42, 2-44, Comparative Examples 2-2-2- In the samples 4 and 2-8, 66 nylon (Amilan CM3001-N) manufactured by Toray Industries, Inc. was used and injection molding was performed at a resin temperature of 295 ° C.

  The samples of Examples 2-4, 2-12, 2-16, 2-20, 2-24, 2-28, 2-36, 2-40, 2-43 and 2-45 are manufactured by Mitsubishi Chemical Corporation. Injection molding was performed at a resin temperature of 230 ° C. using PTEE elastomer resin (Primalloy B1600N).

  The samples of Examples 2-5 to 2-8, 2-29 to 2-33, and 2-46 subjected to the above-described treatment were fixed with heat-resistant tape so as to come into contact with the types of resin plates shown in Table 1. Then, a sample fixed with heat-resistant tape is placed on a heating body set to the resin melting point (or meltable temperature) of each resin, and the sample is pressurized with a load of 9 kgf from above and thermally fused. Thus, an iron alloy article sample having the same shape as the iron alloy article sample obtained by the injection molding described above was obtained. The details of the resin plate used are shown below.

In Examples 2-5 and 2-29, the resin plate of ABS resin (Stylac (R) -ABS General Purpose 026) manufactured by Asahi Kasei Chemicals Co., Ltd. was used to fix the sample to the shape described above, and the obtained sample was An iron alloy article sample was obtained by placing on a heating body set at 230 ° C. and heat-sealing.
In Example 2-30, a heating element in which a resin plate of PC / ABS resin (Iupilon MB2215R) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was fixed to have the above-described shape and the obtained sample was set at 260 ° C. An iron alloy article sample was obtained by placing it on and heat-sealing.
In Examples 2-6, 2-31 and 2-46, 66 nylon (Amilan CM3001-N) manufactured by Toray Industries, Inc. was used to fix the sample to the shape described above, and the obtained sample was 290 ° C. An iron alloy article sample was obtained by placing it on a heating body set to 1 and heat-sealing.
In Examples 2-7 and 2-32, using a resin plate of PPS resin (Fortron PPS 1140A64) manufactured by Polyplastics Co., Ltd., it was fixed so as to have the above-mentioned shape, and the obtained sample was set at 320 ° C. An iron alloy article sample was obtained by placing on the heated body and heat-sealing.
In Examples 2-8 and 2-33, a PTFE elastomer resin (Primalloy B1600N) resin plate manufactured by Mitsubishi Chemical Corporation was used to fix the sample to the shape described above, and the resulting sample was heated to 230 ° C. An iron alloy article sample was obtained by placing on the body and heat-sealing.

  Next, the samples of Comparative Examples 2-5 and 2-6 were prepared using an epoxy resin-based adhesive that has been conventionally known to be excellent in peel resistance as a comparative example of a 90-degree peel strength test described later. It was produced by the procedure.

  About the sample of Comparative Examples 2-5 and 2-6 which provided the coating | cover of the above-mentioned alkoxysilane containing triazine thiol derivative, Cemedine Co., Ltd. make two-component room temperature curing epoxy resin adhesive (EP330) was apply | coated. And to the samples of Comparative Examples 2-5 and 2-6, a resin plate of PTEE elastomer resin (Primalloy B1600N) manufactured by Mitsubishi Chemical Corporation was adhered and left at room temperature for 24 hours to obtain an iron alloy article sample. .

(5) Strength Evaluation According to Examples 1-1 to 1-3, 2-1 to 2-46, Comparative Examples 1-1, 1-2, and 2-1 to 2-8 obtained in this manner. The strength of the iron alloy sample was evaluated.
Examples 1-1 to 1-3, 2-1 to 2-3, 2-5 to 2-7, 2-9 to 2-11, 23-13 to 2-15, 2-17 to 2-19, 2-21 to 2-23, 2-25 to 2-27, 2-29 to 2-32, 2-34, 2-35, 2-37 to 2-40, 2-42, 2-44, 2- 46 and Comparative Examples 1-1, 1-2, 2-1 to 2-4, 2-7, and 2-8 were used as tensile test pieces, and the bonding strength was evaluated by a tensile test.
Examples 2-4, 2-8, 2-12, 2-16, 2-20, 2-24, 2-28, 2-33, 2-36, 2-41, 2-43, 2- 45 and Comparative Examples 2-5 and 2-6 were used as 90-degree peel test pieces, and the peel strength was evaluated by a 90-degree peel test.

  For the tensile test, an autograph AG-10TD tester manufactured by Shimadzu Corporation was used, and the iron plate part (iron alloy base material) of the iron alloy article sample and the terminal part of the resin plate part (resin) (terminal part on the opposite side of the joint part) Each was gripped with a flat chuck and pulled at a pulling speed of 5 mm / min until breaking. The stress obtained by dividing the maximum ultimate load up to the break by the joining area (length 12 mm × width 20 mm) was defined as joining strength (tensile shear strength). The test was performed three times for each sample.

  Further, in the 90-degree peel test, the metal substrate is fixed using a fixing jig so that the iron plate portion (iron alloy base material) of the iron alloy article sample and the joint surface of the resin are horizontal. Is held at a distance of 100 mm / min by moving the flat chuck in a direction that forms an angle of 90 degrees with the joint surface. The stress obtained by dividing the load by the joining length (length: 20 mm) was determined. The test was performed three times for each sample.

  Table 2 shows the shear strength measurement results of Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2. The results in Table 2 show the maximum and minimum values of tests performed three times for each sample.

In Table 3, Examples 2-1 to 2-3, 2-5 to 2-7, 2-9 to 2-11, 23-13 to 2-15, 2-17 to 2-19, 2-21 to 2 -23, 2-25 to 2-27, 2-29 to 2-32, 2-34, 2-35, 2-37 to 2-40, 2-42, 2-44, 2-46 and Comparative Example 2 The shear strength of the iron alloy article samples of -1 to 2-4, 2-7, and 2-8 is shown. Examples 2-4, 2-8, 2-12, 2-16, 2-20, 2-24, 2-28, 2-33, 2-36, 2-41, 2-43, 2- Table 3 also shows the 90 degree peel strength of the iron alloy article samples of No. 45 and Comparative Examples 2-5 and 2-6.
The strengths in Table 3 show the average value of the results of three tests for each sample.

In the tensile test, all of the example samples showed excellent tensile shear strength of 2.8 MPa (27.5 kgf / cm ² ) or more. On the other hand, all of the comparative example samples subjected to the tensile test did not have any strength. In the example sample, the fracture was confirmed at the joint surface or the resin part. Furthermore, regarding the fracture surface (iron alloy plate side) at the joint surface, resin adhesion was observed, and it was confirmed that a part of the fracture occurred in the resin.

  In addition, all of the example samples subjected to the 90 degree peel test had a 90 degree peel strength of 2.5 N / mm or more, while all of the comparative samples had a 90 degree peel strength of 1.5 N / mm or less. . That is, the example sample showed 90 degree peel strength clearly higher than the comparative example sample.

  This application claims priority to a Japanese patent application whose application number is Japanese Patent Application No. 2008-164221. Japanese Patent Application No. 2008-164221 is incorporated herein by reference.

Claims (14)

An iron alloy article comprising a substrate made of iron or an iron alloy, and a resin bonded to at least a part of the surface of the substrate via a dehydrated silanol-containing triazine thiol derivative coating,
Between the substrate and the dehydrated silanol-containing triazine thiol derivative coating, at least one selected from the group consisting of hydroxide, carboxylate, phosphate, sulfate, thiosulfate, chloride and perchloride An iron alloy article comprising a metal compound film containing   The iron alloy article according to claim 1, wherein the phosphate is at least one selected from the group consisting of a metal hydrogen phosphate, a metal dihydrogen phosphate, and a metal phosphate.   The phosphate group is composed of zinc phosphate, zinc hydrogen phosphate, manganese phosphate, manganese hydrogen phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium phosphate, sodium calcium phosphate, iron phosphate and zirconium phosphate. The iron alloy article according to claim 1, wherein at least one selected from the group consisting of:   The iron alloy article according to claim 1, wherein the sulfate is iron sulfate or chromium sulfate or both. A method for producing an iron alloy article, wherein a resin is bonded to at least a part of an iron alloy substrate made of iron or an iron alloy using an alkoxysilane-containing triazine thiol derivative,
At least part of the surface of the iron alloy substrate is composed of carboxylic acid, carboxylate, phosphoric acid, phosphate, sulfuric acid, sulfate, thiosulfate, hydrochloric acid, chloride, perchloric acid and perchlorate. Forming a metal compound film using a solution containing at least one selected from the group;
Contacting the metal compound film with an alkoxysilane-containing triazine thiol derivative;
The manufacturing method characterized by including the process of joining resin to the part which contacted the said alkoxysilane containing triazine thiol derivative.   6. The production method according to claim 5, wherein the solution contains at least one selected from phosphoric acid, a metal hydrogen phosphate, a metal dihydrogen phosphate, and a metal phosphate.   The solution contains at least one selected from zinc phosphate, zinc hydrogen phosphate, manganese phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, sodium calcium phosphate, calcium phosphate and zirconium phosphate. The manufacturing method according to claim 5. A base made of iron or an iron alloy, and an iron alloy member in which at least a part of the surface of the base is coated with a dehydrated silanol-containing triazine thiol derivative or a silanol-containing triazine thiol derivative,
Between the substrate and the dehydrated silanol-containing triazine thiol derivative coating or the silanol-containing triazine thiol derivative coating, hydroxide, carboxylate, phosphate, sulfate, thiosulfate, chloride and perchlorate An iron alloy member comprising a metal compound film containing at least one selected from the group consisting of:   The iron alloy member according to claim 8, wherein the phosphate is at least one selected from the group consisting of a metal hydrogen phosphate, a metal dihydrogen phosphate, and a metal phosphate.   The phosphate group is composed of zinc phosphate, zinc hydrogen phosphate, manganese phosphate, manganese hydrogen phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium phosphate, sodium calcium phosphate, iron phosphate and zirconium phosphate. The iron alloy member according to claim 8, wherein at least one selected from the group consisting of:   The iron alloy member according to claim 8, wherein the sulfate is iron sulfate or a metal sulfate. A method for producing an iron alloy member comprising contacting an alkoxysilane-containing triazine thiol derivative with at least a part of an iron alloy substrate made of iron or an iron alloy,
At least part of the surface of the iron alloy substrate is composed of carboxylic acid, carboxylate, phosphoric acid, phosphate, sulfuric acid, sulfate, thiosulfate, hydrochloric acid, chloride, perchloric acid and perchlorate. Forming a metal compound film using a solution containing at least one selected from the group;
And a step of bringing the metal compound film into contact with an alkoxysilane-containing triazine thiol derivative.   The manufacturing method according to claim 12, wherein the solution contains at least one selected from phosphoric acid, metal hydrogen phosphate, metal dihydrogen phosphate, and metal phosphate.   The solution includes at least one selected from zinc phosphate, zinc hydrogen phosphate, manganese phosphate, manganese hydrogen phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, sodium calcium phosphate, calcium phosphate, and zirconium phosphate. The manufacturing method according to claim 12.

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